US4271008A - Production of ethylene - Google Patents

Production of ethylene Download PDF

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Publication number
US4271008A
US4271008A US06/098,609 US9860979A US4271008A US 4271008 A US4271008 A US 4271008A US 9860979 A US9860979 A US 9860979A US 4271008 A US4271008 A US 4271008A
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gas mixture
sub
aluminum
reaction
heated
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US06/098,609
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Wilhelm Vogt
Hermann Glaser
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Hoechst AG
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Hoechst AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B01J19/0026—Avoiding carbon deposits
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/04—Thermal processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/949—Miscellaneous considerations
    • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

  • This invention relates to a process for making ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to a hydropyrolysis reaction.
  • a process for making ethane and/or ethylene has been described, wherein a reaction mixture consisting of hydrocarbons, carbon monoxide, carbon dioxide, water and hydrogen (the mixture being obtained by reacting hydrogen with carbon monoxide in a molar ratio of 1:1 to 5:1 in contact with a Fischer-Tropsch catalyst containing iron, cobalt, nickel or ruthenium) is pyrolyzed inside a hydropyrolyzing zone at a temperature of 600° to 900° C., under a pressure of at least 5 bars and over a period of 0.1 to 60 seconds, and the resulting gas mixture issuing from the hydropyrolyzing zone is treated so as to separate C 2 -hydrocarbons therefrom.
  • a reaction mixture consisting of hydrocarbons, carbon monoxide, carbon dioxide, water and hydrogen (the mixture being obtained by reacting hydrogen with carbon monoxide in a molar ratio of 1:1 to 5:1 in contact with a Fischer-Tropsch catalyst containing iron, cobalt, nickel or ruthenium
  • a quartz tube should conveniently be used for subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to hydropyrolysis therein.
  • a quartz tube it has been possible to effect the reaction over a period of 250 hours substantially without undesirable disturbing deposition of carbon black. If carried out in a tube made up, e.g. of iron, temperature-resistant steels or nickel, the reaction just described is normally accompanied by undesirable formation of carbon black or decomposition of hydrocarbons.
  • the present invention relates more particularly to a process for the commercial production of ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and water to a pyrolysis reaction permitting the formation of carbon black (which may ultimately result in the tubular reactors becoming clogged therewith) and decomposition of hydrocarbons to be substantially avoided.
  • the invention provides for the gas mixture to be heated to temperatures higher than 800° C. inside a reaction zone having metal walls containing aluminum and/or copper in at least their surface portions facing and coming into contact with the gas mixture.
  • Materials which can be used for making the walls of the reaction zone comprise chrome and chrome-nickel steels which additionally contain aluminum, e.g. ALUCHROM (this is a registered Trade Mark; construction materials nos. 1.4765 and 1,4767 according to DIN-specification (DIN stands for German Industrial Standard) 17 470, July 1963); ARMCO 18 SR (this is a registered Trade Mark) or KANTHAL (this is a registered Trade Mark).
  • ALUCHROM this is a registered Trade Mark
  • ARMCO 18 SR this is a registered Trade Mark
  • KANTHAL this is a registered Trade Mark
  • One method of applying aluminum to the inside walls of a reaction zone comprises filling the zone with a mixture of pulverulent or granular aluminum and a porous carrier which does not react with aluminum, e.g. aluminum oxide, and annealing the mixture at 700° to 1000° C. under scavenging treatment with a mixture of nitrogen and aluminum chloride in vapor form. During that treatment which is effected over a period of 2 to 5 hours, it is possible for sufficient aluminum to diffuse into, and catalytically inactivate, the metal walls of the reaction zone.
  • Another method of applying aluminum to the inside walls of the reactor comprises filling the reactor with an aluminum melt of 700° to 900° C. and leaving the walls in contact therewith over 2 to 20 hours.
  • Another method of reliably reducing the catalytic activity of metal walls comprises using the aluminum in further admixture with copper powder, copper granules or a copper melt, and contacting the metal walls therewith.
  • Still another method of reducing the catalytic activity of reactor inside walls comprises using the gas mixture in further admixture with one or more sulfur-containing compounds, e.g. H 2 S, CS 2 and COS, and contacting the metal walls therewith.
  • one or more sulfur-containing compounds e.g. H 2 S, CS 2 and COS
  • the gas mixture used in each particular case was left uncooled and, after pressure release to 1 bar, it was introduced into a hydropyrolysis reactor of which the tubular structures which were heated over a length of 20 cm had an internal diameter of 10 mm.
  • the various materials used for making the tubular structures are indicated in the following Table 2.
  • the residence time of the gas mixture in the tubular structures was about 0.25 second, under the experimental conditions selected (1 bar; 890° C.). In Examples 13 to 22 listed in Table 2, the change in volume varied by about -10%.

Abstract

The invention relates to a process for making ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to a hydropyrolysis reaction. More particularly, the gas mixture is heated to temperatures higher than 800 DEG C. inside a reaction zone having metal walls. The walls contain aluminum and/or copper in at least their surface portions.

Description

This invention relates to a process for making ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to a hydropyrolysis reaction.
A process for making ethane and/or ethylene has been described, wherein a reaction mixture consisting of hydrocarbons, carbon monoxide, carbon dioxide, water and hydrogen (the mixture being obtained by reacting hydrogen with carbon monoxide in a molar ratio of 1:1 to 5:1 in contact with a Fischer-Tropsch catalyst containing iron, cobalt, nickel or ruthenium) is pyrolyzed inside a hydropyrolyzing zone at a temperature of 600° to 900° C., under a pressure of at least 5 bars and over a period of 0.1 to 60 seconds, and the resulting gas mixture issuing from the hydropyrolyzing zone is treated so as to separate C2 -hydrocarbons therefrom. For effecting the hydropyrolysis reaction just described, use can be made of a reactor which has a heat-resistant steel cylinder placed therein, which faces and comes into contact with the reaction mixture. As to those mixtures which are obtained by the catalytic reduction of carbon monoxide with hydrogen by a process, such as described in British Patent Specification Nos. 1,515,604, 1,554,082 and 1,548,527, respectively, it is only possible for them to be subjected to hydropyrolysis provided that equilibrium establishment for the following reactions
H.sub.2 +CO.sub.2 →H.sub.2 O+CO
--CH.sub.2 --+H.sub.2 O→CO+2H.sub.2
--CH.sub.2 --+2CO.sub.2 →3CO+H.sub.2 O
is avoided at the necessary temperature range of about 800° to 950° C. and also provided that neither the hydrocarbons nor carbon monoxide produce carbon black in quantities which are liable to adversely affect operation.
Unless catalytically promoted by contact of the reaction mixture with the wall of the pyrolysis reactor, the above reactions occur so reluctantly that they cannot reasonably be said to impair the yield of olefins formed by hydropyrolysis during the necessary short contact time of 0.02 to 2 seconds.
It has also been described that a quartz tube should conveniently be used for subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to hydropyrolysis therein. In a quartz tube, it has been possible to effect the reaction over a period of 250 hours substantially without undesirable disturbing deposition of carbon black. If carried out in a tube made up, e.g. of iron, temperature-resistant steels or nickel, the reaction just described is normally accompanied by undesirable formation of carbon black or decomposition of hydrocarbons.
The present invention relates more particularly to a process for the commercial production of ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and water to a pyrolysis reaction permitting the formation of carbon black (which may ultimately result in the tubular reactors becoming clogged therewith) and decomposition of hydrocarbons to be substantially avoided.
To this end, the invention provides for the gas mixture to be heated to temperatures higher than 800° C. inside a reaction zone having metal walls containing aluminum and/or copper in at least their surface portions facing and coming into contact with the gas mixture.
Preferred features of the present process provide:
(a) for the gas mixture to be heated to temperatures higher than 900° C.;
(b) for the gas mixture to be heated to temperatures up to 1000° C.;
(c) for the heated gas mixture to be maintained under a pressure of less than 5 bars;
(d) for the heated gas mixture to be maintained under a pressure within the range 1.5 to 4 bars;
(e) for the metal walls of the reaction zone to be made up of steel containing aluminum and/or copper;
(f) for the metal walls of the reaction zone to have aluminum and/or copper applied thereto;
(g) for the aluminum and/or copper to be applied to the metal walls via the gas phase with the use of one or more halogen compounds as transporting agent;
(h) for the aluminum and/or copper to be applied to the metal walls by contacting the latter with an aluminum and/or copper melt; and
(i) for the gas mixture to be used in further admixture with one or more gaseous sulfur compounds.
Materials which can be used for making the walls of the reaction zone comprise chrome and chrome-nickel steels which additionally contain aluminum, e.g. ALUCHROM (this is a registered Trade Mark; construction materials nos. 1.4765 and 1,4767 according to DIN-specification (DIN stands for German Industrial Standard) 17 470, July 1963); ARMCO 18 SR (this is a registered Trade Mark) or KANTHAL (this is a registered Trade Mark). In those cases in which steel substantially free from aluminum is used for making the walls of the reaction zone, it is necessary for aluminum to be applied to that side of the walls which faces and comes into contact with the gas mixture. Even aluminum-containing steel should have additional aluminum applied thereto as this permits the catalytic activity of the reactor walls to be further reduced.
One method of applying aluminum to the inside walls of a reaction zone comprises filling the zone with a mixture of pulverulent or granular aluminum and a porous carrier which does not react with aluminum, e.g. aluminum oxide, and annealing the mixture at 700° to 1000° C. under scavenging treatment with a mixture of nitrogen and aluminum chloride in vapor form. During that treatment which is effected over a period of 2 to 5 hours, it is possible for sufficient aluminum to diffuse into, and catalytically inactivate, the metal walls of the reaction zone.
Another method of applying aluminum to the inside walls of the reactor comprises filling the reactor with an aluminum melt of 700° to 900° C. and leaving the walls in contact therewith over 2 to 20 hours. Another method of reliably reducing the catalytic activity of metal walls comprises using the aluminum in further admixture with copper powder, copper granules or a copper melt, and contacting the metal walls therewith.
Still another method of reducing the catalytic activity of reactor inside walls comprises using the gas mixture in further admixture with one or more sulfur-containing compounds, e.g. H2 S, CS2 and COS, and contacting the metal walls therewith.
EXAMPLES
In all of the following Examples, use was made of a gas mixture which was obtained by contacting a mixture of carbon monoxide and hydrogen which were used in a ratio by volume of 1:1, at 290° C. and under 16 bars with a carrier-supported catalyst containing iron, copper and potassium. The composition typical of the gas mixture is indicated in the following Table 1, left hand column.
The gas mixture used in each particular case was left uncooled and, after pressure release to 1 bar, it was introduced into a hydropyrolysis reactor of which the tubular structures which were heated over a length of 20 cm had an internal diameter of 10 mm. The various materials used for making the tubular structures are indicated in the following Table 2. The residence time of the gas mixture in the tubular structures was about 0.25 second, under the experimental conditions selected (1 bar; 890° C.). In Examples 13 to 22 listed in Table 2, the change in volume varied by about -10%.
As would appear to result from Table 2, comparative Examples 1 to 12, the tubular structures made from the materials specified were found to promote the formation of carbon black (which results in the tubular structures becoming ultimately clogged therewith) and/or to effect an increase in the CO-content and/or to produce reaction gas of low ethylene concentration.
This is in clear contrast with the results obtained with tubular structures made from materials in accordance with this invention (Examples 13 to 22). Reaction gas of high ethylene concentration was obtained. Even after prolonged operation, carbon black could not be found to have been formed. Nor could the CO-concentration be found to have been significantly increased, based on the CO-concentration of the feed gas mixture.
The analytical data typical of a gas obtained by the present hydropyrolysis process is indicated in Table 1, right hand portion.
In Table 2, the sign "a→b" indicates that the concentration in the hydropyrolysis gas changed from (a) to (b) volume % during the experiment.
              TABLE 1                                                     
______________________________________                                    
             Hydropyrolysis gas                                           
Gas mixture                   C - %                                       
Com-               Com-    Yield    based on                              
posi-    Selec-    posi-   %, based sum of                                
tion     tivity    tion    on CO    hydro-                                
vol. %   %         vol. %  reacted  carbons                               
______________________________________                                    
H.sub.2 O                                                                 
     2.85                2.79                                             
O.sub.2                                                                   
     0.59                0.48                                             
N.sub.2                                                                   
     0.24                0.24                                             
H.sub.2                                                                   
     26.42               29.62                                            
CO   14.33               13.48                                            
CO.sub.2                                                                  
     34.32         46.51 31.34     47.12      --                          
CH.sub.4                                                                  
     12.80         17.35 12.89     19.48      36.84                       
C.sub.2 H.sub.2                                                           
     <0.01               0.37      1.12       2.11                        
C.sub.2 H.sub.4                                                           
     0.59          9.27  6.84      20.67      39.10                       
C.sub.2 H.sub.6                                                           
     2.32                0.53      1.60       3.03                        
C.sub.3                                                                   
     2.41          9.80  0.59      2.67       5.06                        
C.sub.4                                                                   
     2.35          12.74 0.12      0.37       1.37                        
C.sub.5                                                                   
     0.54          3.66  0.26                                             
C.sub.6                                                                   
     0.15          1.22  0.09                                             
C.sub.7                                                                   
     0.04          0.38  0.25      6.76       12.78                       
C.sub.8                                                                   
     <0.02         <0.22 0.07                                             
C.sub.8+                                                                  
     <0.02         ˜0.22                                            
                         ˜0.04                                      
______________________________________                                    

                                  TABLE 2                                 
__________________________________________________________________________
                   Operation    content                                   
Material used for making                                                  
                   period                                                 
                         CO-increase                                      
                                vol. %                                    
tubular structure  (h)   vol. % CH.sub.4                                  
                                     C.sub.2 H.sub.4                      
                                          observations                    
__________________________________________________________________________
(Comparative Examples)                                                    
1 Iron             14    18 → 0                                    
                                17   4.2  clogged by                      
2 Iron, S-treated  24    4 → 0                                     
                                16 → 9                             
                                     5.9 → 0.4                     
                                          carbon black                    
3 Iron, P-treated  4      5 → 20                                   
                                13   6 → 0.7                       
4 Iron, treated with                                                      
                   6     10     15   6 → 3.5                       
  silicic acid ester                                                      
5 Iron, treated with                                                      
                   18    16 → 2                                    
                                11 → 8                             
                                     2.8 → 0.4                     
  silicic acid ester;                                                     
  annealed for 4 h                                                        
6 Iron, treated with                                                      
                   3      5 → 15                                   
                                12 → 17                            
                                     5.5 → 18                      
  silicic acid ester; annealed                                            
  for 4 h sulfided gas mixture                                            
7 Iron, gold-plated                                                       
                   22    30     9    1.5                                  
  with H(AuCl.sub.4)                                                      
8 Steel; material no.                                                     
                   19    3      12.8 5.9  carbon black                    
  1.4016                                  formation                       
  (CEKAS; Reg. Trade -ark)                                                
9 Steel; material no.                                                     
                   21    1      15.2 6.0  carbon black                    
  1.4016 (CEKAS; Reg. Trade Mark);        formation                       
  sulfided gas mixture                                                    
10                                                                        
  Steel; material no.                                                     
                   22    16     10.6 1.1                                  
  1.4841                                                                  
11                                                                        
  Steel; material no.                                                     
                   12    18     12   4.2 → 2.0                     
  1.4541 -12       Pure nickel, polished                                  
                         16     11   22.4 1.0 carbon black                
                                          formation                       
(Examples in accordance with                                              
invention)                                                                
13                                                                        
  ALUCHROM O       250   0.5    16   6.2  spontaneous                     
14                                                                        
  ALUCHROM O; sulfided                                                    
                   250   0      14.8 5.7  ethylene drop                   
  gas mixture                             after 89 h                      
15                                                                        
  ALUCHROM W       92    0      14.6 7.1                                  
16                                                                        
  KANTHAL DSD      250   0      12.2 5.25                                 
17                                                                        
  INCONEL 601;     250   1      16   6.9                                  
  Al-plated                                                               
18                                                                        
  ARMCO 18 SR      250   2.6    16.8 6.6                                  
19                                                                        
  ARMCO 18 SR; Al-plated                                                  
                   250   1.5    16.8 7.2                                  
20                                                                        
  Steel; material no.                                                     
                   250   0      15.6 6.2                                  
  1.4571 plated with                                                      
  Al and Cu                                                               
21                                                                        
  Steel; material no.                                                     
                   250   0      16.4 6.7                                  
  1.4571; Al-plated                                                       
22                                                                        
  Steel; material no.                                                     
                   250   -3.3   14.3 5.7                                  
  1.4571; Cu-plated                                                       
__________________________________________________________________________

Claims (5)

We claim:
1. A process for making ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to a hydropyrolysis reaction, which comprises heating the gas mixture to temperatures higher than 800° C. and maintaining the heated gas mixture under a pressure of less than 5 bars inside a reaction zone having metal walls made up of steel containing copper.
2. A process for making ethylene by subjecting a gas mixture containing hydrocarbons, hydrogen, carbon monoxide, carbon dioxide and steam to a hydropyrolysis reaction, which comprises heating the gas mixture to temperatures higher than 800° C. and maintaining the heated gas mixture under a pressure of less than 5 bars inside a reaction zone having metal walls coated with an overlayer of at least one metal selected from copper and aluminum, said overlayer being applied to the metal walls via the gas phase with the use of at least one halogen compound as a transporting agent.
3. The process as claimed in claim 1 or 2, wherein the gas mixture is heated to temperatures of 900°-1000° C.
4. The process as claimed in claim 1 or 2, wherein the heated gas mixture is maintained under a pressure of 1.5-4 bars.
5. The process as claimed in claim 1 or 2, wherein the gas mixture is used in further admixture with at least one gaseous sulfur compound.
US06/098,609 1978-12-04 1979-11-29 Production of ethylene Expired - Lifetime US4271008A (en)

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Application Number Priority Date Filing Date Title
DE2852314 1978-12-04
DE19782852314 DE2852314A1 (en) 1978-12-04 1978-12-04 METHOD FOR PRODUCING ETHYLENE

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JP (1) JPS5579328A (en)
CA (1) CA1111075A (en)
DE (2) DE2852314A1 (en)
ZA (1) ZA796546B (en)

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US4527003A (en) * 1983-03-03 1985-07-02 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking process for producing olefins from hydrocarbons
US4545893A (en) * 1984-07-20 1985-10-08 Phillips Petroleum Company Antifoulants for thermal cracking processes
US4575413A (en) * 1984-07-06 1986-03-11 Exxon Research & Engineering Co. Aluminum stearate and/or acetate antifoulants for refinery operations
US4599478A (en) * 1983-02-18 1986-07-08 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking method for producing olefines from hydrocarbons
US4599480A (en) * 1985-07-12 1986-07-08 Shell Oil Company Sequential cracking of hydrocarbons
US4725349A (en) * 1984-04-13 1988-02-16 Mitsubishi Jukogyo Kabushiki Kaisha Process for the selective production of petrochemical products
US5575902A (en) * 1994-01-04 1996-11-19 Chevron Chemical Company Cracking processes
US5593571A (en) * 1993-01-04 1997-01-14 Chevron Chemical Company Treating oxidized steels in low-sulfur reforming processes
US5674376A (en) * 1991-03-08 1997-10-07 Chevron Chemical Company Low sufur reforming process
US5723707A (en) * 1993-01-04 1998-03-03 Chevron Chemical Company Dehydrogenation processes, equipment and catalyst loads therefor
US5849969A (en) * 1993-01-04 1998-12-15 Chevron Chemical Company Hydrodealkylation processes
US6258256B1 (en) 1994-01-04 2001-07-10 Chevron Phillips Chemical Company Lp Cracking processes
US6274113B1 (en) 1994-01-04 2001-08-14 Chevron Phillips Chemical Company Lp Increasing production in hydrocarbon conversion processes
US6419986B1 (en) 1997-01-10 2002-07-16 Chevron Phillips Chemical Company Ip Method for removing reactive metal from a reactor system
US20030135077A1 (en) * 2002-01-14 2003-07-17 O'rear Dennis J. Olefin production from low sulfur hydrocarbon fractions
USRE38532E1 (en) 1993-01-04 2004-06-08 Chevron Phillips Chemical Company Lp Hydrodealkylation processes
WO2010059224A1 (en) * 2008-11-19 2010-05-27 Global Energies, Llc Low co2 emissions system

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US2621216A (en) * 1950-08-17 1952-12-09 Shell Dev Production of ethylene
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US2621216A (en) * 1950-08-17 1952-12-09 Shell Dev Production of ethylene
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599478A (en) * 1983-02-18 1986-07-08 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking method for producing olefines from hydrocarbons
US4599479A (en) * 1983-03-03 1986-07-08 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking process for producing olefins from hydrocarbons
US4527003A (en) * 1983-03-03 1985-07-02 Mitsubishi Jukogyo Kabushiki Kaisha Thermal cracking process for producing olefins from hydrocarbons
US4725349A (en) * 1984-04-13 1988-02-16 Mitsubishi Jukogyo Kabushiki Kaisha Process for the selective production of petrochemical products
US4575413A (en) * 1984-07-06 1986-03-11 Exxon Research & Engineering Co. Aluminum stearate and/or acetate antifoulants for refinery operations
US4545893A (en) * 1984-07-20 1985-10-08 Phillips Petroleum Company Antifoulants for thermal cracking processes
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EP0011874A1 (en) 1980-06-11
JPS5579328A (en) 1980-06-14
CA1111075A (en) 1981-10-20
DE2852314A1 (en) 1980-06-26
ZA796546B (en) 1980-11-26
DE2962847D1 (en) 1982-07-01
EP0011874B1 (en) 1982-05-12

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